Photographic developer



said ring member forming a hydrogenized ring Patented June 27, 1939UNITED STATES PATENT rno'roGEArmo DEVELOPER No Drawing.

Application March 19, 1937, Serial No. 131,780. In Germany April 23,1936 12 Claims.

Our present invention relates to a process of ucts develop the latentsilver image in presence developing photographic silver halide emulsionsand more particularly to a process in which the developing agent used isa derivative of an organic diamine, one amino-group of said diaminecarrying a ring member, such as for instance CHrCHrCHr, (EH-CHz-CHz,(III-CH2. CH;'S-

CH: CH:

together with the carbon-atom in ortho-position of the substitutedamino-group or with the other Another object of our invention relates todeveloping colored pictures with the aid of said compounds.

The invention is based on the observation that v such diamines oi thebenzene series are valuable developing agents in which at least oneaminogroup is a member of a hydrogenized nucleus and the secondamino-group is. in such a position to the other that formation ofquinonoid compounds becomes possible. In other words we may use forinstance tetrahydroquinoxaline:

- Saminodihydro-l-methyliridole on \CHCH: 4 Q

s CH: Mmino-S-methoxy-l:2:3:4-tctrabydmquinaldine HsN V NH

Samimbe'nlothiamline and substitution products thereof. These odofalkali with or without a sulfite more powerfully than the knownpara-phenylenediamine and produce a very fine grain. For the purpose ofob-- taining special gradation the substances may be I used inintermixture with each other or with a known developer. In combinationwith substances suitable for color development such as for instancephenyl-m'e'thyl-pyrazolone, a-hY- droxy-naphthoic' acid,phenyl-isoxazolone and the chloranilide of benzoyl acetic ester, theyare also useful particularly when the amino-group is in thepara-position to the nuclear amino-group fortl'fe color development ofsingle layer or multilayer photographic material.

The following examples illustrate developers suitable for the invention?Example 1 A developer suitable for very fine grain work consists of thefollowing solution: I

The developer according to Example 3 produces in addition to'the silverimage a dyestufi image 7 in blue-red, from which by means of a suitable,Water cubic-centimeters 100 v Tetrahydroquinoxaline "grains" 1.5Calcined sodium carbonate do 3 Anhydrous sodium sulfite do.. 3

' Example 2* Water cubic centimeters..- 100 6-amino-8-methoxy1,2,3,4-tetrahydroquinoline gram 1 Calcined sodium carbonate grams 3Anhydrous sodium sulfite do.. 3

Example 3 ZWater cubic centimeters 100 6-amino-8-methoxyl,2,3,4-tetrahydroquinaldine gram 1 Calcined sodium carbonate gramsu 31-phenyl-3-methyl-5-pyrazolonegram; 0.5

. Example 4 Water cubic centimeters' 100 5-amino-dihydromethylindolegram 1 Calcined sodium carbonate grams 3 Anhydrous sodium sulfite do 3 HExample 5 I Water; cubic centimeters 100 Calcined sodium carbonate gramsI 3 5-aminobenzothiazoline gram 1 By using other components instead or!the 1- phenyl-3-methyl-5-pyrazolone other colored images maybeobtained.- Our invention is not limited to the examples given, but wecontemplate as included all such modifications and equivalentsspecification.

By introducing the coupling component into the individual layers of amulti-layer material a 3- color image can be produced by developmenteither by the negative process or by the reversal process, the imagebeing in complementary colors in the first case and in correct colors inthe secondcase.

The methylene group or groups concerned in the ring formation may carrysubstituents which may be of a character suitable for lending solubilityto the developer, such as for instance the hydroxy group andhydroxy-ethyl group.

What we claim is:

l. A process of developing photographic silver halide emulsions whichcomprises treating the said material in an aqueous solution oftetrahydroquinoxaline sodium carbonate and sodium sufite.

2. A process of developing photographic silver halide emulsions whichcomprises treating the said material in an aqueous solution of B-amino-8 methoxy 1,2,3,4-tetrahydroquinoline, sodium carbonate and sodiumsulfite.

3. A process of developing photographic silver halide emulsions whichcomprises treating the said material in an aqueous solution of 6-amino-8methoxy 1,2,3,4 tetrahydroquinaldine, sodium carbonate andl-phenyl-3-methyl-pyrazolone.

4. As a composition of matter, a photographic developer containingtetrahydroquinoxaline sodium carbonate and sodium sulfite.

5. As a composition of matter, a photographic developer containing6-amino-8-methoxy-1,2,13,4- tetrahydroquinoline sodium carbonate andsodium sulfite.

6. As a composition of matter, a photographic developer containing6-amino-8-methoxy-1,23,4- tetrahydroquinaldine sodium carbonate and 1-phenyI-B-methyl-pyrazolone.

7. A process of developing photographic silver halide emulsions, whichcomprises treating said emulsions in a bath containing a heterocyclicdiamine of the benzene series hydrogenized in the heterocyclic nucleusselected from the group consisting of 5-aminodihydroindoles,G-aminotetrahydroquinolines, '5-aminobenzothiazolines,tetrahydroquinoxalines, and alkyland oxalkyl substitution productsthereof.

8. As a composition of matter a photographic developer containing analkali metal sulfite, an alkali metal carbonate and a heterocyclicdiamine of the benzene series hydrogenized in the heterocyclic nucleus,said diamine being selected from the group consisting of5-aminodihydroindoles, 6- aminotetrahydroquinolines,fi-aminobenzothiazolines, tetrahydroquinoxalines, and alkyland oxalkylsubstitution products thereof.

9. As a composition of matter a photographic developer for color formingdevelopment containing an alkali metal sulfite, an alkali metalcarbonwherein Y is selected from the group consisting of -CH2CH2, -CH2,S;

Z is a member of the group consisting of H,

-OCHa;

,R1 is a member of the group consisting of -CHs,

said developer being capable of forming a dyestuff with a dyestuffcomponent for color forming development.

10. A process of developing silver halide emulsions, which comprisestreating said material in a bath containing a diamine of the benzeneseries corresponding to the following general formula wherein Y is amember of the group consisting of CH2- CH2, CH2, S;

Z is a member of the group consisting of H,

OCH: and CH3;

R1 is a member of the group consisting of CH3,

H, CH2.CH2.OH.

11. A process of developing silver halide emulsions, which comprisestreating said material in a bath containing a diamine of the benzeneseries corresponding to the following general formula Y Haw-W whereinsaid diamine being used in combination with a dyestufi component forcolor forming development.

12. As a composition of matter a photographic developer comprising analkali metal sulfite, an alkali metal carbonate and a compound cor-.responding to the following general formula wherein Y is a member ofthe group consisting of CH2- CH2, CH2, S;

Z is a member of the group consisting of H,

OCH3 and CH3;

R1 is a member of the group consisting of CH3.

H, CH2.CH2.OH.

